JPH0122238B2 - - Google Patents
Info
- Publication number
- JPH0122238B2 JPH0122238B2 JP26990084A JP26990084A JPH0122238B2 JP H0122238 B2 JPH0122238 B2 JP H0122238B2 JP 26990084 A JP26990084 A JP 26990084A JP 26990084 A JP26990084 A JP 26990084A JP H0122238 B2 JPH0122238 B2 JP H0122238B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- palladium
- oxide
- metallized layer
- ceramics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000919 ceramic Substances 0.000 claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 19
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 16
- 229910052763 palladium Inorganic materials 0.000 claims description 13
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229940116318 copper carbonate Drugs 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims description 7
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000001465 metallisation Methods 0.000 claims description 5
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 37
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 16
- 239000011247 coating layer Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- -1 hydride compound Chemical class 0.000 description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 3
- 229910003446 platinum oxide Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 235000007173 Abies balsamea Nutrition 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004857 Balsam Substances 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 244000018716 Impatiens biflora Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- XPPWAISRWKKERW-UHFFFAOYSA-N copper palladium Chemical compound [Cu].[Pd] XPPWAISRWKKERW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PCEXQRKSUSSDFT-UHFFFAOYSA-N [Mn].[Mo] Chemical compound [Mn].[Mo] PCEXQRKSUSSDFT-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Ceramic Products (AREA)
Description
技術分野
本発明は、セラミツクスの簡便なメタライズ法
に関する。
発明の背景
一般に、セラミツクスは、耐熱性、耐摩耗性、
絶縁性等に優れる反面脆く衝撃に弱いため、構造
材料として用いられるときには、金属との接合体
にして使用されることが多い。金属とセラミツク
スを接合する場合には、先ずセラミツクス表面を
メタライズする必要がある。また、セラミツクス
を導電材料として用いる場合には、セラミツクス
表面にメタライズを行つて使用されている。
セラミツクスのメタライズ法としては、テレフ
ンケン法、活性金属法、水素化合物法、酸化物ソ
ルダー法、炭酸銀法等が知られているが、これら
の内テレフンケン法以外の方法には工程が複雑で
あるのに加えて、メタライズ層の接着強度、耐熱
衝撃性、耐化学薬品性等が充分でない場合がある
ため、現在のところテレフンケン法によるのが一
般的である。テレフンケン法は、セラミツクス表
面にモリブデン−マンガンを被覆し、非酸化性雰
囲気中1400〜1700℃という高温で焼付け、その上
に金属メツキを行い、更に被膜の安定化のために
再度非酸化性雰囲気中で加熱することによりメタ
ライズし、次いで必要に応じて金属をロウ接する
ものである。しかし、この方法には、作業工程が
長く且つ煩雑であるという大きな欠点があるのに
加えて、加熱温度が高いという欠点もある。
本発明者は、上記欠点が解消されたセラミツク
スのメタライズ法を開発するため鋭意研究した結
果、炭酸銅、硫酸銅、硫化銅、酸化銅及び塩化銅
の少なくとも１種とSiO2又はカオリンとの混合
物を被覆層として用いる場合には空気等の酸化性
雰囲気中にて比較的低温で焼付けができ、次いで
焼付け層を還元処理すれば極めて簡便にメタライ
ズできること、SiO2又はカオリンの併用により
メタライズ層の均一性特に表面の平滑性及び光沢
が向上すること、得られたメタライズ層は導電性
に優れ且つ接着強度が高いこと等を見出し、これ
らの知見に基づく発明については別途特許出願し
た（特願昭58−83721号及び特願昭58−131575
号）。
而して、本発明者は、引き続く研究において、
上記混合物に更にパラジウム、酸化パラジウム及
び塩化白金の少なくとも１種を併用することによ
りメタライズ層の接着強度及び耐化学薬品性が顕
著に向上することを見出し、本発明を完成するに
至つた。
発明の構成及び効果
本発明は、炭酸銅、硫酸銅、硫化銅、酸化銅及
び塩化銅の少なくとも１種、SiO2又は（及び）
カオリン、並びにパラジウム、酸化パラジウム及
び塩化白金の少なくとも１種からなる混合物を、
セラミツクス表面に被覆し、酸化性雰囲気中900
〜1300℃で加熱して焼付けた後、焼付け層を還元
処理することを特徴とするセラミツクスのメタラ
イズ法に係る。
本発明においては、被覆層としてSiO2又は
（及び）カオリンを併用したことにより、焼付け
被覆のむらが防止でき、メタライズ層の均一性特
に表面の平滑性及び光沢が向上しているのみなら
ず、被覆層として更にパラジウム、酸化パラジウ
ム及び塩化白金の少なくとも１種を併用したこと
により、メタライズ層の接着強度及び耐化学薬品
性が顕著に向上している。
本発明において被覆層として用いる炭酸銅、硫
酸銅、硫化銅、酸化銅及び塩化銅は、いずれも通
常粉末状のものを使用する。粉末の粒度として
は、特に限定されないが、通常100μｍ以下程度
好ましくは50μｍ以下程度が適当である。
本発明において被覆層として用いる酸化パラジ
ウムとしては、PdO、Pd2O3、PdO2等を、又塩
化白金としてはPtCl2、PtCl4等を挙げることがで
き、これらのいずれも使用できる。
また、SiO2、カオリン、パラジウム、酸化パ
ラジウム及び塩化白金も、通常粉末状のものを使
用する。粒度は上記と同様である。
各成分の使用割合は炭酸銅、硫酸銅、硫化銅、
酸化銅及び塩化銅の少くとも１種80〜30重量％程
度に対してSiO2又は（及び）カオリンを５〜30
重量％程度好ましくは５〜20重量％、パラジウ
ム、酸化パラジウム及び塩化白金の少なくとも１
種を10〜60重量％程度好ましくは20〜50重量％と
するのが適当である。SiO2又は（及び）カオリ
ンが５重量％未満の場合にはメタライズ層表面の
平滑性及び光沢が不充分になることがあり、30重
量％を越えた場合にはメタライズ層の導電性が低
下する傾向があるので好ましくない。又、パラジ
ウム、酸化パラジウム及び塩化白金の少なくとも
１種が10重量％未満の場合及び60重量％を越えた
場合には、いずれもメタライズ層の接着強度の向
上が不充分な傾向にあるので好ましくない。
本発明においては、炭酸銅、硫酸銅、硫化銅、
酸化銅及び塩化銅の少なくとも１種、SiO2又は
（及び）カオリン、並びにパラジウム、酸化パラ
ジウム及び塩化白金の少なくとも１種の混合物を
粉末状のまま使用しても良いし、適当なバインダ
ー及びその溶剤、例えばスクリーンオイル等の印
刷用インキ、バルサム等を適宜の量用いてペース
ト状にして使用しても良い。
粉末状又はペースト状の混合物をメタライズが
必要なセラミツクス表面に撤布又は塗布して被覆
する。被覆する量は、特に限定されず、所望のメ
タライズ層の厚さに応じて、適宜決定される。次
に、上記で被覆されたセラミツクスを酸化性雰囲
気中にて加熱して被覆層を焼付ける。酸化性雰囲
気としては、特殊なものを使用する必要はなく、
空気、空気と窒素との混合気等を使用すれば充分
である。また、加熱条件としては、セラミツクス
の形状、大きさや用いた被覆層の種類、被覆量等
により変化するが、通常900〜1300℃の温度で５
〜60分間程度加熱する。この加熱により炭酸銅、
硫酸銅、硫化銅又は塩化銅は酸化されて酸化銅
に、パラジウムは酸化されて酸化パラジウムに、
塩化白金は酸化されて酸化白金になり、酸化銅と
酸化パラジウム又は（及び）酸化白金とを主体と
する被膜がセラミツクスに密着する。この際、酸
化銅の融液がセラミツクス内に一部浸透すること
により得られるメタライズ層の接着強度が高めら
れる。又、パラジウム、酸化パラジウム及び塩化
白金の少なくとも１種を併用したことによつて得
られるメタライズ層の接着強度及び耐化学薬品性
が顕著に向上している。更に、SiO2又は（及び）
カオリンを使用したことによりメタライズ層の均
一性、表面の平滑性及び光沢が著しく高められ
る。加熱温度が900℃より低い場合は上記浸透が
起こらず接着強度が不充分になり、又1300℃より
高い場合は被覆層の粘性が低下して流出すること
があるので好ましくない。
次に、上記により焼付け層が施されたセラミツ
クスを還元処理する。還元方法としては、特に限
定されず、酸化銅、酸化パラジウム及び酸化白金
がそれぞれ金属銅、パラジウム及び白金に還元さ
れるならばどんな方法でも良く、例えば水素雰囲
気、一酸化炭素雰囲気等の還元性雰囲気中での加
熱、エタノール、メタノール、プロパノール等の
アルコール類、ベンジン、ホルマリン等の還元性
溶媒への浸漬、ジメチルアミンボラン水溶液への
浸漬等を挙げることができる。還元性雰囲気中で
加熱する場合の温度は、焼付け層の分解、変質等
を防ぐために前記焼付け温度よりも低いことが好
ましく、通常200〜900℃程度とし、時間は通常５
〜60分間程度とする。また、還元性溶媒への浸漬
による場合は、セラミツクスを通常200〜500℃程
度好ましくは300℃前後に加熱後、上記還元性溶
媒に10〜60秒間程度浸漬すれば良い。また、ジメ
チルアミンボラン水溶液への浸漬による場合は、
セラミツクスを通常40〜60℃程度に加熱後、該水
溶液に10〜60秒間程度浸漬すれば良い。
上記還元処理により、極めて優れた導電性を有
する銅−パラジウム又は（及び）白金メタライズ
層がセラミツクス表面に形成される。
斯くしてメタライズされたセラミツクスには、
必要に応じて、常法例えばロウ接等により、各種
金属を容易に接合することができる。
本発明によりメタライズできるセラミツクスと
しては、特に限定されず、例えば窒化珪素、サイ
アロン、炭化珪素、窒化アルミニウム等の非酸化
物系セラミツクス、アルミナ、ジルコニア、ムラ
イト、ベリリア、マグネシア、コージーライト等
の酸化物系セラミツクスを挙げることができる。
本発明によれば、従来法に比べて低温で焼付け
後、還元処理するという極めて簡便な操作で、セ
ラミツクス表面にメタライズ層が形成でき、得ら
れたメタライズ層は導電性に優れ且つ接着強度及
び耐化学薬品性が極めて高く、またメタライズ層
の均一性、特に表面の平滑性及び光沢に優れてい
るので商品価値が高いという効果が得られる。
本発明によりメタライズされたセラミツクス
は、上記の如き性能を有するので、セラミツクス
パツケージ、IC基板のプリント配線等の電子部
品、セラミツクスを用いた耐摩耗性部品、耐熱性
部品等に好適に使用できる。
実施例
以下、実施例を挙げて、本発明を更に具体的に
説明する。
実施例 １
酸化銅粉末（粒度5μｍ）45重量％とパラジウ
ム粉末（粒度5μｍ）45重量％とSiO2粉末（粒度
5μｍ）10重量％を混合したもの100重量部に対し
てバルサム10重量部を混合してペースト状とし、
これを平板正方形の窒化珪素（Si3N4）、サイア
ロン、炭化珪素（SiC）、アルミナ又はジルコニ
アの焼結体の表面に0.1ｇ／cm2塗布した。次に、
電気炉を用い空気中にて1100℃で20分間焼成して
焼付け被覆層を形成した。引続き焼成したものを
乾燥器中で50℃に加熱した後、ジメチルアミンボ
ランの５％水溶液中に浸漬した。これによつて焼
付け被覆層が還元され、金属銅−パラジウムのメ
タライズ層が形成された。下記第１表に還元前後
における、1000Vの電圧で測定した電気抵抗値を
示した。還元後のメタライズ層は、極めて優れた
導電性を有していることが判つた。
かくして得たメタライズ層を有する各セラミツ
クスと銅片とを銀ロウを用いてロウ接し、秤量
2ton及び荷重速度５mm／minの引張試験器を用い
て、メタライズ層の接着強度を測定したところ、
いずれも極めて強く接着されていることが判つ
た。結果を下記第１表に併記した。
TECHNICAL FIELD The present invention relates to a simple method for metallizing ceramics. Background of the Invention Ceramics are generally known for their heat resistance, abrasion resistance,
Although it has excellent insulation properties, it is brittle and weak against impact, so when used as a structural material, it is often used in the form of a bonded body with metal. When joining metal and ceramics, it is first necessary to metalize the surface of the ceramics. Furthermore, when ceramics are used as a conductive material, the surface of the ceramics is metallized. Known methods for metallizing ceramics include the Telefunken method, active metal method, hydride compound method, oxide solder method, and silver carbonate method, but methods other than the Telefunken method have complicated processes. In addition, the adhesive strength, thermal shock resistance, chemical resistance, etc. of the metallized layer may not be sufficient, so the Telefunken method is generally used at present. In the Telefunken method, the ceramic surface is coated with molybdenum-manganese, baked at a high temperature of 1400 to 1700°C in a non-oxidizing atmosphere, plated with metal, and then coated again in a non-oxidizing atmosphere to stabilize the coating. The material is metallized by heating, and then the metal is brazed if necessary. However, this method has the major disadvantage that the working process is long and complicated, and also has the disadvantage that the heating temperature is high. As a result of intensive research to develop a ceramic metallization method that eliminates the above-mentioned drawbacks, the present inventor has developed a mixture of at least one of copper carbonate, copper sulfate, copper sulfide, copper oxide, and copper chloride with SiO 2 or kaolin. When used as a coating layer, it can be baked at a relatively low temperature in an oxidizing atmosphere such as air, and then the baked layer can be reduced to make metallization extremely easy, and the combination of SiO 2 or kaolin can improve the uniformity of the metallized layer. They found that the properties, especially the surface smoothness and gloss, were improved, and that the obtained metallized layer had excellent conductivity and high adhesive strength, and a separate patent application was filed for an invention based on these findings (Japanese patent application filed in 1983). -83721 and patent application 1982-131575
issue). Therefore, in subsequent research, the present inventor
The present inventors have discovered that the adhesion strength and chemical resistance of the metallized layer can be significantly improved by further adding at least one of palladium, palladium oxide, and platinum chloride to the above mixture, and have completed the present invention. Structure and effects of the invention The present invention provides at least one of copper carbonate, copper sulfate, copper sulfide, copper oxide, and copper chloride, SiO 2 or (and)
A mixture consisting of kaolin and at least one of palladium, palladium oxide and platinum chloride,
900% coated on the ceramic surface in an oxidizing atmosphere
The present invention relates to a ceramic metallization method characterized by heating and baking at ~1300°C and then subjecting the baked layer to reduction treatment. In the present invention, by using SiO 2 or (and) kaolin in combination as a coating layer, it is possible to prevent unevenness in the baked coating, improve the uniformity of the metallized layer, especially the surface smoothness and gloss, and improve the coating. By further using at least one of palladium, palladium oxide, and platinum chloride in the layer, the adhesive strength and chemical resistance of the metallized layer are significantly improved. Copper carbonate, copper sulfate, copper sulfide, copper oxide and copper chloride used as the coating layer in the present invention are all usually in powder form. The particle size of the powder is not particularly limited, but it is usually about 100 μm or less, preferably about 50 μm or less. Examples of palladium oxide used as the coating layer in the present invention include PdO, Pd 2 O 3 and PdO 2 , and examples of platinum chloride include PtCl 2 and PtCl 4 , and any of these can be used. Further, SiO 2 , kaolin, palladium, palladium oxide, and platinum chloride are also usually used in powder form. The particle size is the same as above. The usage ratio of each component is copper carbonate, copper sulfate, copper sulfide,
About 80 to 30% by weight of at least one of copper oxide and copper chloride, and 5 to 30% of SiO 2 or (and) kaolin.
about 5% to 20% by weight, at least one of palladium, palladium oxide and platinum chloride
It is appropriate that the amount of seeds be about 10 to 60% by weight, preferably 20 to 50% by weight. If SiO 2 or (and) kaolin is less than 5% by weight, the surface smoothness and gloss of the metallized layer may become insufficient, and if it exceeds 30% by weight, the conductivity of the metallized layer will decrease. I don't like it because it has a tendency. Furthermore, if at least one of palladium, palladium oxide, and platinum chloride is present in an amount less than 10% by weight or more than 60% by weight, the adhesive strength of the metallized layer tends to be insufficiently improved, which is undesirable. . In the present invention, copper carbonate, copper sulfate, copper sulfide,
A mixture of at least one of copper oxide and copper chloride, SiO 2 or (and) kaolin, and at least one of palladium, palladium oxide and platinum chloride may be used in powder form, or a suitable binder and its solvent may be used. For example, printing ink such as screen oil, balsam, etc. may be used in an appropriate amount to form a paste. A powdered or paste-like mixture is coated by spreading or coating the ceramic surface that requires metallization. The amount of coating is not particularly limited, and is appropriately determined depending on the desired thickness of the metallized layer. Next, the ceramic coated above is heated in an oxidizing atmosphere to bake the coating layer. There is no need to use a special oxidizing atmosphere;
It is sufficient to use air, a mixture of air and nitrogen, or the like. The heating conditions vary depending on the shape and size of the ceramic, the type of coating layer used, the amount of coating, etc., but are usually at a temperature of 900 to 1300℃.
Heat for ~60 minutes. This heating causes copper carbonate,
Copper sulfate, copper sulfide or copper chloride is oxidized to copper oxide, palladium is oxidized to palladium oxide,
Platinum chloride is oxidized to become platinum oxide, and a coating mainly consisting of copper oxide and palladium oxide or/and platinum oxide adheres to the ceramic. At this time, the adhesive strength of the metallized layer obtained is increased by partially penetrating the copper oxide melt into the ceramics. Further, by using at least one of palladium, palladium oxide, and platinum chloride in combination, the adhesive strength and chemical resistance of the metallized layer obtained are significantly improved. Furthermore, SiO 2 or (and)
The use of kaolin significantly improves the uniformity, surface smoothness and gloss of the metallized layer. If the heating temperature is lower than 900°C, the above-mentioned permeation will not occur and the adhesive strength will be insufficient, and if it is higher than 1300°C, the viscosity of the coating layer will decrease and it may flow out, which is not preferred. Next, the ceramics on which the baked layer has been applied as described above is subjected to a reduction treatment. The reduction method is not particularly limited, and any method may be used as long as copper oxide, palladium oxide, and platinum oxide are reduced to metallic copper, palladium, and platinum, respectively, such as a reducing atmosphere such as a hydrogen atmosphere or a carbon monoxide atmosphere. Examples include heating in a vacuum, immersion in alcohols such as ethanol, methanol, and propanol, reducing solvents such as benzine and formalin, and immersion in an aqueous dimethylamine borane solution. When heating in a reducing atmosphere, the temperature is preferably lower than the baking temperature to prevent decomposition and alteration of the baked layer, and is usually about 200 to 900°C, and the time is usually about 5.
~60 minutes. Further, in the case of immersion in a reducing solvent, the ceramics may be heated usually to about 200 to 500°C, preferably around 300°C, and then immersed in the reducing solvent for about 10 to 60 seconds. In addition, when immersed in dimethylamine borane aqueous solution,
Ceramics may be heated to about 40 to 60°C and then immersed in the aqueous solution for about 10 to 60 seconds. By the above reduction treatment, a copper-palladium or/and platinum metallized layer having extremely excellent conductivity is formed on the ceramic surface. Ceramics metalized in this way have
If necessary, various metals can be easily joined by conventional methods such as brazing. Ceramics that can be metallized according to the present invention are not particularly limited, and include non-oxide ceramics such as silicon nitride, sialon, silicon carbide, and aluminum nitride, and oxide ceramics such as alumina, zirconia, mullite, beryllia, magnesia, and cordierite. Ceramics can be mentioned. According to the present invention, a metallized layer can be formed on the ceramic surface by an extremely simple operation of baking at a lower temperature and then performing a reduction treatment than in the conventional method, and the obtained metallized layer has excellent conductivity, adhesive strength, and durability. It has extremely high chemical resistance, and the metallized layer has excellent uniformity, especially surface smoothness and gloss, so it has a high commercial value. Since the ceramics metallized according to the present invention has the above-mentioned performance, it can be suitably used for ceramic packages, electronic components such as printed wiring of IC boards, wear-resistant parts using ceramics, heat-resistant parts, etc. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 45% by weight of copper oxide powder (particle size: 5 μm), 45% by weight of palladium powder (particle size: 5 μm), and SiO 2 powder (particle size:
Mix 10 parts by weight of balsam with 100 parts by weight of 10% by weight (5 μm) to form a paste,
This was applied at 0.1 g/cm 2 onto the surface of a flat square sintered body of silicon nitride (Si 3 N 4 ), Sialon, silicon carbide (SiC), alumina, or zirconia. next,
A baked coating layer was formed by baking in air at 1100°C for 20 minutes using an electric furnace. The calcined product was then heated to 50° C. in a dryer and then immersed in a 5% aqueous solution of dimethylamine borane. This reduced the baked coating layer and formed a metallized layer of metallic copper-palladium. Table 1 below shows the electrical resistance values measured at a voltage of 1000V before and after reduction. It was found that the metallized layer after reduction had extremely excellent electrical conductivity. Each ceramic having a metallized layer thus obtained and a copper piece were soldered using silver solder, and weighed.
The adhesive strength of the metallized layer was measured using a tensile tester with a load rate of 2 tons and a loading rate of 5 mm/min.
It was found that both were extremely strongly bonded. The results are also listed in Table 1 below.
【表】
上記で得た各セラミツクスのメタライズ層の耐
化学薬品性を調べるため、48％KOH水溶液中で
70℃、72時間の浸漬試験をしたが変色、導電性、
接着強度等の変化は全く認められなかつた。
また、得られたメタライズ層は均一性特に表面
の平滑性及び光沢が優れており、商品価値の高い
ものであつた。
実施例 ２
パラジウム粉末に代えて酸化パラジウム
（PdO）粉末（粒度5μｍ）を用いた他は、実施例
１と同様にして下記第２表の結果を得た。[Table] In order to investigate the chemical resistance of the metallized layer of each ceramic obtained above,
I did an immersion test at 70℃ for 72 hours, but there was no discoloration, conductivity,
No changes in adhesive strength etc. were observed at all. Furthermore, the obtained metallized layer had excellent uniformity, particularly surface smoothness and gloss, and had high commercial value. Example 2 The results shown in Table 2 below were obtained in the same manner as in Example 1, except that palladium oxide (PdO) powder (particle size 5 μm) was used instead of palladium powder.
【表】
第２表から、メタライズ層の導電性が極めて優
れ、接着強度が極めて高いことが明らかである。
上記で得た各セラミツクスのメタライズ層の耐
化学薬品性を調べるため、48％KOH水溶液中で
70℃、72時間の浸漬試験をしたが変色、導電性、
接着強度等の変化は全く認められなかつた。
また、得られたメタライズ層は均一性特に表面
の平滑性及び光沢が優れており、商品価値の高い
ものであつた。
実施例 ３
パラジウム粉末に代えて塩化白金（PtCl2）（粒
度5μｍ）を用いた他は、実施例１と同様にして
下記第３表の結果を得た。[Table] From Table 2, it is clear that the metallized layer has extremely good conductivity and extremely high adhesive strength. In order to investigate the chemical resistance of the metallized layer of each ceramic obtained above, we tested it in a 48% KOH aqueous solution.
I did an immersion test at 70℃ for 72 hours, but there was no discoloration, conductivity,
No changes in adhesive strength etc. were observed at all. Furthermore, the obtained metallized layer had excellent uniformity, particularly surface smoothness and gloss, and had high commercial value. Example 3 The results shown in Table 3 below were obtained in the same manner as in Example 1, except that platinum chloride (PtCl 2 ) (particle size 5 μm) was used in place of palladium powder.
【表】
第３表から、メタライズ層の導電性が極めて優
れ、接着強度が極めて高いことが明らかである。
上記で得た各セラミツクスのメタライズ層の耐
化学薬品性を調べるため、48％KOH水溶液中で
70℃、72時間の浸漬試験をしたが変色、導電性、
接着強度等の変化は全く認められなかつた。
また、得られたメタライズ層は均一特性に表面
の平滑性及び光沢が優れており、商品価値の高い
ものであつた。
比較例 １
酸化銅粉末（粒度5μｍ）90重量％とSiO2（粒度
5μｍ）10重量％との混合粉末100重量部を使用す
る以外は実施例１と同様にしてペーストを調製
し、実施例１と同様にして各種セラミツクスのメ
タライズを行なつた。
次いで、得られたメタライズ層を有する各セラ
ミツクスと銅片とを実施例１と同様にしてロウ接
し、メタライズ層の接着強度を測定した。結果を
第４表に示す。
第４表
セラミツクス 接着強度
（Kg／cm2）
窒化珪素 450
サイアロン 470
炭化珪素 415
アルミナ 640
ジルコニア 660
第１表乃至第３表と第４表とを対比すれば、本
発明方法に従つて、パラジウム、酸化パラジウム
または塩化白金を配合することにより、メタライ
ズ層の接着強度が大巾に改善されることが明らか
である。[Table] From Table 3, it is clear that the metallized layer has extremely good conductivity and extremely high adhesive strength. In order to investigate the chemical resistance of the metallized layer of each ceramic obtained above, we tested it in a 48% KOH aqueous solution.
I did an immersion test at 70℃ for 72 hours, but there was no discoloration, conductivity,
No changes in adhesive strength etc. were observed at all. Furthermore, the obtained metallized layer had excellent uniformity, surface smoothness and gloss, and had high commercial value. Comparative Example 1 Copper oxide powder (particle size 5 μm) 90% by weight and SiO 2 (particle size
A paste was prepared in the same manner as in Example 1, except that 100 parts by weight of the mixed powder with 10% by weight of 5 μm) was used, and various ceramics were metallized in the same manner as in Example 1. Next, each ceramic having the obtained metallized layer and a copper piece were brazed together in the same manner as in Example 1, and the adhesive strength of the metallized layer was measured. The results are shown in Table 4. Table 4: Ceramics Adhesive Strength (Kg/cm 2 ) Silicon Nitride 450 Sialon 470 Silicon Carbide 415 Alumina 640 Zirconia 660 Comparing Tables 1 to 3 with Table 4, palladium, palladium, It is clear that the adhesion strength of the metallized layer is greatly improved by incorporating palladium oxide or platinum chloride.
Claims (1)
の少なくとも１種、SiO2又は（及び）カオリン、
並びにパラジウム、酸化パラジウム及び塩化白金
の少なくとも１種からなる混合物を、セラミツク
ス表面に被覆し、酸化性雰囲気中900〜1300℃で
加熱して焼付けた後、焼付け層を還元処理するこ
とを特徴とするセラミツクスのメタライズ法。1 At least one of copper carbonate, copper sulfate, copper sulfide, copper oxide and copper chloride, SiO 2 or (and) kaolin,
Furthermore, the ceramic surface is coated with a mixture consisting of at least one of palladium, palladium oxide, and platinum chloride, and after being baked by heating at 900 to 1300°C in an oxidizing atmosphere, the baked layer is subjected to a reduction treatment. Ceramics metallization method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26990084A JPS61146778A (en) | 1984-12-20 | 1984-12-20 | Metallization of ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26990084A JPS61146778A (en) | 1984-12-20 | 1984-12-20 | Metallization of ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61146778A JPS61146778A (en) | 1986-07-04 |
| JPH0122238B2 true JPH0122238B2 (en) | 1989-04-25 |
Family
ID=17478778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26990084A Granted JPS61146778A (en) | 1984-12-20 | 1984-12-20 | Metallization of ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61146778A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113929865A (en) * | 2021-11-22 | 2022-01-14 | 山东一诺威聚氨酯股份有限公司 | High-thermal-conductivity low-abrasion TPU material and preparation method thereof |
-
1984
- 1984-12-20 JP JP26990084A patent/JPS61146778A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61146778A (en) | 1986-07-04 |
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